US4041019A - Delayed-action, heat activated-urethane catalyst - Google Patents
Delayed-action, heat activated-urethane catalyst Download PDFInfo
- Publication number
- US4041019A US4041019A US05/624,698 US62469875A US4041019A US 4041019 A US4041019 A US 4041019A US 62469875 A US62469875 A US 62469875A US 4041019 A US4041019 A US 4041019A
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- United States
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- hydrogen
- hydrocarbyl
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- Expired - Lifetime
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical group 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 12
- -1 aliphatic polyol Chemical class 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 9
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 3
- 125000003118 aryl group Chemical group 0.000 claims 2
- 125000002837 carbocyclic group Chemical group 0.000 claims 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 abstract description 23
- 150000002513 isocyanates Chemical class 0.000 abstract description 17
- 239000004814 polyurethane Substances 0.000 abstract description 9
- 229920002635 polyurethane Polymers 0.000 abstract description 9
- 230000001737 promoting effect Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 5
- 125000004008 6 membered carbocyclic group Chemical group 0.000 abstract description 3
- 125000001054 5 membered carbocyclic group Chemical group 0.000 abstract description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical group 0.000 description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 239000000376 reactant Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- 150000003673 urethanes Chemical class 0.000 description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- ADAKRBAJFHTIEW-UHFFFAOYSA-N 1-chloro-4-isocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1 ADAKRBAJFHTIEW-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FYWJWWMKCARWQG-UHFFFAOYSA-N 1,2-dichloro-3-isocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1Cl FYWJWWMKCARWQG-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- ONEKMHWIMFXASJ-UHFFFAOYSA-N 1-butyl-2-isocyanatobenzene Chemical compound CCCCC1=CC=CC=C1N=C=O ONEKMHWIMFXASJ-UHFFFAOYSA-N 0.000 description 1
- NOHQUGRVHSJYMR-UHFFFAOYSA-N 1-chloro-2-isocyanatobenzene Chemical compound ClC1=CC=CC=C1N=C=O NOHQUGRVHSJYMR-UHFFFAOYSA-N 0.000 description 1
- QLOQTKGUQKAAAB-UHFFFAOYSA-N 1-isocyanato-2-(2-isocyanatoethoxy)ethane Chemical compound O=C=NCCOCCN=C=O QLOQTKGUQKAAAB-UHFFFAOYSA-N 0.000 description 1
- SUVCZZADQDCIEQ-UHFFFAOYSA-N 1-isocyanato-2-methoxybenzene Chemical compound COC1=CC=CC=C1N=C=O SUVCZZADQDCIEQ-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- DYQFCTCUULUMTQ-UHFFFAOYSA-N 1-isocyanatooctane Chemical compound CCCCCCCCN=C=O DYQFCTCUULUMTQ-UHFFFAOYSA-N 0.000 description 1
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- NAPDOWNULRULLI-UHFFFAOYSA-N 2-benzyl-1h-imidazole Chemical compound C=1C=CC=CC=1CC1=NC=CN1 NAPDOWNULRULLI-UHFFFAOYSA-N 0.000 description 1
- JDLHQBAZAFNBPQ-UHFFFAOYSA-N 2-benzyl-5-methyl-1h-imidazole Chemical compound CC1=CNC(CC=2C=CC=CC=2)=N1 JDLHQBAZAFNBPQ-UHFFFAOYSA-N 0.000 description 1
- SLLDUURXGMDOCY-UHFFFAOYSA-N 2-butyl-1h-imidazole Chemical compound CCCCC1=NC=CN1 SLLDUURXGMDOCY-UHFFFAOYSA-N 0.000 description 1
- LYNVLWLRSACENL-UHFFFAOYSA-N 2-decyl-1h-imidazole Chemical compound CCCCCCCCCCC1=NC=CN1 LYNVLWLRSACENL-UHFFFAOYSA-N 0.000 description 1
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- VNPRJHMMOKDEDZ-UHFFFAOYSA-L 6-methylheptyl 2-[dibutyl-[2-(6-methylheptoxy)-2-oxoethyl]sulfanylstannyl]sulfanylacetate Chemical compound CC(C)CCCCCOC(=O)CS[Sn](CCCC)(CCCC)SCC(=O)OCCCCCC(C)C VNPRJHMMOKDEDZ-UHFFFAOYSA-L 0.000 description 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000287433 Turdus Species 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical compound C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LGDNSGSJKBIVFG-UHFFFAOYSA-N n,n-dimethyl-2-piperazin-1-ylethanamine Chemical compound CN(C)CCN1CCNCC1 LGDNSGSJKBIVFG-UHFFFAOYSA-N 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
- C08G18/168—Organic compounds
Definitions
- This invention pertains to new catalysts for promoting the reaction between organic isocyanates and organic compounds bearing active hydrogen (i.e., active in the Zerewitinoff test).
- the new catalysts are particularly useful in promoting the reaction of organic isocyanates with aliphatic hydroxyl compounds to produce urethanes.
- Reactions of isocyanates with compounds bearing active hydrogen are well known. This type of reaction is used, for example, to produce urethanes (i.e. carbamates), ureas, etc. Commercially, the most important reaction is in the production of polyurethanes by the reaction of ployisocyanates with aliphatic polyols.
- 1,4-diazabicyclo[2.2.2]octane This particular compound as well as certain other tertiary amines are very effective. Indeed, 1,4-diazabicyclo[2.2.2]octane is so effective that the "pot life" of the reaction mixture is very short and this presents a processing problem in commercial applications (such as carpet foam-backing, etc.) which require that the reaction mixture be doctorable for a period of time.
- Erner et al. described a class of imidazole catalysts in U.S. Pat. No. 3,152,094 that was said to be unreactive in the mixture of urethane reactants at ambient temperatures but highly effective catalysts at moderately elevated temperatures (e.g. about 75° C.). These catalysts were represented by the formula ##STR2## wherein R 2 is hydrogen, alkyl or benzyl; R 1 and R 3 are hydrogen, alkyl, benzyl, or joined to form a 6-membered carbocyclic ring, provided that the total number of carbon atoms in the substituents R 1 , R 2 and R 3 does not exceed 12.
- the disclosure of Erner et al. (U.S. Pat. No. 3,152,094) is hereby incorporated by reference.
- n is an integer of from 1 to 3;
- R 1 is an n-valent organic radical
- R 2 is hydrogen, hydrocarbyl or inertly-substituted hydrocarbyl
- R 3 and R 4 are each independently hydrogen, hydrocarbyl, inertly-substituted hydrocarbyl, or, R 3 and R 4 are joined to form a 5- or 6-membered carbocyclic ring.
- the catalysts are delayed-action, heat-activated catalysts which are particularly useful in the preparation of urethanes.
- the new catalysts are conveniently prepared by reacting an organic isocyanate bearing from 1 to 4 isocyanato groups with an imidazole.
- This reaction is represented by the following equation ##STR4##
- the above reaction is a very facile reaction. Normally it is conducted by merely blending the reactants in essentially stoichiometric amounts at room temperature under substantially anhydrous conditions.
- an inert solvent e.g. methylene chloride
- slightly elevated temperatures e.g. up to about 50°C. may be used to increase the rate of reaction between certain combinations of isocyanates and imidazoles.
- the new catalysts are normally solid compounds and are subject to hydrolysis. Prolonged contact with moist air will result, for example, in the slow hydrolytic decomposition of the compounds. Therefore, normal precautions should be used in storing and handling the catalysts to prevent such decomposition.
- the isocyanate reactants used in forming the instant class of catalyst are represented by III above.
- Such isocyanate reactants form a known class of compounds having many members; any member of which can be used herein.
- isocyanates examples include methyl isocyanate, ethyl isocyanate, butyl isocyanate, octyl isocyanate, octadecyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, thiodiethylene diisocyanate, oxydiethylene diisocyanate, phenyl isocyanate, toluene diisocyanate, methylene diphenyl diisocyanate, polymethylene polyphenyl isocyanate, chlorophenyl isocyanate, dichlorophenyl isocyanate, benzylphenyl diisocyanate, methoxyphenyl isocyanate, butylphenyl isocyanate, vinyl isocyanate, cyclohexyl isocyanate those represented by the formula ##STR5## where R' 1 is hydrogen or C 1 to C 4 alkyl
- Any organic isocyanate bearing from 1 to 4 isocyanato groups can be used in this reaction.
- the imidazoles represented by formula (IV) above, likewise form a known class of compounds having many members; any member of which can be suitably used herein.
- suitable such imidazoles include imidazole, 2-methyl imidazole, 2-butyl imidazole, 2-decyl imidazole, 4-methyl imidazole, 5-methyl imidazole, 4,5-dimethyl imidazole, benzimidazole, 2-benzyl imidazole, 2-benzyl-4-methyl imidazole, and the like.
- 2-Methyl imidazole is the most preferred imidazole for use in preparing our new catalysts.
- the instant class of catalysts are used in small but catalytic amounts in promoting the reaction between organic isocyanates and organic compounds bearing active hydrogen and reactive with the isocyanates. Normally, amounts of from about 0.1 to about 20 weight percent, based on the weight of isocyanate reactant, is sufficient to yield an acceptable reaction rate at an elevated temperature.
- any polyol conventionally employed in the preparation of urethanes can be employed in the process of the present invention.
- Such polyols include polyether polyols, polyester polyols, and the like or mixtures thereof.
- polyols are described in the literature, as illustrated by "Polyurethanes: Chemistry and Technology, parts I and II", by Saunders and Frisch, Interscience, 1964.
- Particularly suitable polyols include polyether polyols having from 2 to 4 hydroxyl groups per molecule and an average molecular weight of from about 3,000 to about 7,000.
- Any organic polyisocyanate conventionally employed in the preparation of urethanes can be employed in the process of the instant invention.
- This also includes isocyanato-containing prepolymers prepared by reacting various polyols with polyisocyanates and thus producing a product having residual isocyanate groups.
- Such polyisocyanates are likewise described in the Saunders and Frisch publication mentioned above and also in the patent literature. See, for example, Robins (U.S. Pat. No. 3,583,945), Kamal & Rogier (U.S. Pat. No. 3,455,883), etc.
- Particularly suitable polyisocyanates include, for example, toluene diisocyanate, methylene diphenyl diisocyanate, and polymethylene polyphenyl isocyanates
- the thermally curable polyurethane composition may likewise comprise blowing or foaming agents, cell control agents, amine and/or organo-metal catalysts, inert fillers, and the like. Such ingredients are likewise discussed in the Saunders and Frisch publication and the patent literature.
- Particularly suitable amine catalysts mentioned therein include, for example, triethylenediamine, N-ethylmorpholine, N-(dimethylaminoethyl)piperazine, N-N'-bis(trimethylaminoethyl)piperazine, tetramethylbutanediamine, dimethylethanolamine, bis(2-dimethyl aminoethyl)ether, mixtures thereof and the like.
- Particularly suitable organo-metal catalysts include stannous octoate, dibutyltin dilaurate, and the like.
- organo-metal catalysts are tin-sulfur catalysts represented by the formula ##STR7## wherein R" 1 and R" 2 are independently hydrocarbon groups having from 1 to about 8 carbon atoms and R" 3 and R" 4 are independently hydrocarbon groups having from 1 to about 18 carbon atoms.
- Such sulfur-containing organo-tin compounds are commercially available from Argus Chemical Corporation as Markure UL-6, Markure UL-29, LRB-1355-331 and LRB-1355-383 and from M and T Chemicals as Thermolite 31.
- a reaction vessel fitted with a thermometer, water condenser, mechanical stirrer and powder-addition funnel was charged with a solution of 500 g (4.2 mol) of phenyl isocyanate in 1 liter of dry methylene chloride.
- the methylene chloride was predried with molecular sieves.
- To this solution was added slowly, and with vigorous stirring, 330 g (4.03 mol) of solid 2-methyl imidazole.
- the 2-methyl imidazole dissolved instantly in the reaction mixture and reacted readily with the phenyl isocyanate.
- the temperature of the reaction mixture rose from ambient to about 30° C. with a white crystalline product precipitating from solution. The temperature of the reaction mixture was then maintained at about 30° C.
- the reaction mixture thus obtained comprised a white crystalline solid suspended in methylene chloride. This mixture was stirred for an additional 2 hours after all of the 2-methyl imidazole was added. The product was subsequently recovered by filtration, washed twice with 300 ml portions of dry carbon tetrachloride (to remove excess phenyl isocyanate), air dried, and placed in a vacuum oven at room temperature for 12 hours. The product thus obtained was a white crystalline solid weighing 750 g (88.0 percent of theory) and melting at a temperature of from 103°-106° C.
- a catalyst corresponding to the structure ##STR8## was prepared by reacting p-chlorophenyl isocyanate with 2-methylimidazole. Two grams of this catalyst was dissolved in 30 ml of tetrahydrofuran (THF). This solution was mixed with 165 g of a urethane prepolymer having an isocyanate equivalent weight of 140. This prepolymer was prepared by reacting an adduct of glycerine and propylene oxide having an average hydroxy equivalent weight of about 86 with toluene diisocyanate in such proportions as to give a product having 30 weight percent reactive isocyanato groups. The THF was subsequently removed from this mixture by vacuum distillation leaving the catalyzed prepolymer as a slightly cloudy liquid.
- THF tetrahydrofuran
- the above catalyzed prepolymer, 166 g was blended with (1) 400 g of a polyether polyol mixture containing (a) 90 weight percent of a glycerine-initiated polyoxypropylene glycol capped with ethylene oxide and having an average molecular weight of 4950 and a hydroxy equivalent weight of 1650; and (b) 10 weight percent of diethylene glycol, and (2) 200 g of alumina trihydrate (marketed by the Reynolds Alumina Company under the designation RH31F). These components were mixed in a Kitchen Aid® K45 mixer and frothed at the highest speed of the K45 mixer for 5 minutes. A froth was thus produced having excellent doctorability. A thin layer, 3/16 inch thick, was doctored (i.e.
- a conventional catalyst e.g. triethylene diamine
- a concentration necessary for the final cure in 15 minutes in a 120° C. oven would have gelled in the bowl of the K45 mixer.
- the following catalysts were used in place of the p-chlorophenyl isocyanate/2-methyl imidazole reaction product in the above formulation.
- Each of the following compounds were effective delayed-action, heat-activated catalysts.
- Compounds 6-10, 12-14 and 16 were particularly effective delayed-action, heat-activated catalysts.
Abstract
New catalysts are described for promoting the reaction of organic isocyanates with organic compounds bearing active hydrogen. These new catalysts correspond to the formula ##STR1## WHEREIN: N IS AN INTEGER OF FROM 1 TO 3; R1 is an n-valent organic radical;
R2 is hydrogen, hydrocarbyl or inertly-substituted hydrocarbyl;
R3 and R4 are each independently hydrogen, hydrocarbyl, inertly-substituted hydrocarbyl, or, R3 and R4 are joined to form a 5- or 6-membered carbocyclic ring. The catalysts are delayed-action, heat-activated catalysts which are particularly useful in the preparation of polyurethanes.
Description
1. Field of the Invention
This invention pertains to new catalysts for promoting the reaction between organic isocyanates and organic compounds bearing active hydrogen (i.e., active in the Zerewitinoff test). The new catalysts are particularly useful in promoting the reaction of organic isocyanates with aliphatic hydroxyl compounds to produce urethanes.
2. Description of the Prior Art
Reactions of isocyanates with compounds bearing active hydrogen are well known. This type of reaction is used, for example, to produce urethanes (i.e. carbamates), ureas, etc. Commercially, the most important reaction is in the production of polyurethanes by the reaction of ployisocyanates with aliphatic polyols.
Various catalysts have been used in promoting the the urethane reaction, but the most common commercial catalyst is 1,4-diazabicyclo[2.2.2]octane. This particular compound as well as certain other tertiary amines are very effective. Indeed, 1,4-diazabicyclo[2.2.2]octane is so effective that the "pot life" of the reaction mixture is very short and this presents a processing problem in commercial applications (such as carpet foam-backing, etc.) which require that the reaction mixture be doctorable for a period of time.
Erner et al. described a class of imidazole catalysts in U.S. Pat. No. 3,152,094 that was said to be unreactive in the mixture of urethane reactants at ambient temperatures but highly effective catalysts at moderately elevated temperatures (e.g. about 75° C.). These catalysts were represented by the formula ##STR2## wherein R2 is hydrogen, alkyl or benzyl; R1 and R3 are hydrogen, alkyl, benzyl, or joined to form a 6-membered carbocyclic ring, provided that the total number of carbon atoms in the substituents R1, R2 and R3 does not exceed 12. The disclosure of Erner et al. (U.S. Pat. No. 3,152,094) is hereby incorporated by reference.
A new class of catalysts has now been discovered having even greater efficiency at latent catalysts in promoting the reaction of isocyanates with compounds bearing active hydrogen. The new class of catalysts is represented by the formula ##STR3## wherein: n is an integer of from 1 to 3;
R1 is an n-valent organic radical;
R2 is hydrogen, hydrocarbyl or inertly-substituted hydrocarbyl;
R3 and R4 are each independently hydrogen, hydrocarbyl, inertly-substituted hydrocarbyl, or, R3 and R4 are joined to form a 5- or 6-membered carbocyclic ring. The catalysts are delayed-action, heat-activated catalysts which are particularly useful in the preparation of urethanes.
The new catalysts, as represented by formula (I), are conveniently prepared by reacting an organic isocyanate bearing from 1 to 4 isocyanato groups with an imidazole. This reaction is represented by the following equation ##STR4## The above reaction is a very facile reaction. Normally it is conducted by merely blending the reactants in essentially stoichiometric amounts at room temperature under substantially anhydrous conditions. The use of an inert solvent (e.g. methylene chloride) is advantageous since this facilitates contact of the reacting moietoes. Likewise, slightly elevated temperatures (e.g. up to about 50°C.) may be used to increase the rate of reaction between certain combinations of isocyanates and imidazoles.
The new catalysts are normally solid compounds and are subject to hydrolysis. Prolonged contact with moist air will result, for example, in the slow hydrolytic decomposition of the compounds. Therefore, normal precautions should be used in storing and handling the catalysts to prevent such decomposition.
The isocyanate reactants used in forming the instant class of catalyst are represented by III above. Such isocyanate reactants form a known class of compounds having many members; any member of which can be used herein. E.g., aliphatic isocyanates, aromatic isocyanates, inertly-substituted aliphatic isocyanates, or inertly-substituted aromatic isocyanates, and the like. Examples of such isocyanates include methyl isocyanate, ethyl isocyanate, butyl isocyanate, octyl isocyanate, octadecyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, thiodiethylene diisocyanate, oxydiethylene diisocyanate, phenyl isocyanate, toluene diisocyanate, methylene diphenyl diisocyanate, polymethylene polyphenyl isocyanate, chlorophenyl isocyanate, dichlorophenyl isocyanate, benzylphenyl diisocyanate, methoxyphenyl isocyanate, butylphenyl isocyanate, vinyl isocyanate, cyclohexyl isocyanate those represented by the formula ##STR5## where R'1 is hydrogen or C1 to C4 alkyl and R'2 is chloro or C1 to C4 alkyl, and ##STR6## R'3 is hydrogen or chloro, and the like. Any organic isocyanate bearing from 1 to 4 isocyanato groups can be used in this reaction. However, due to the very high toxicity of the lower aliphatic isocyanates, we prefer to use isocyanates having at least 6 carbon atoms in R1 and we most prefer to use aromatic isocyanates in preparing our new catalysts.
The imidazoles, represented by formula (IV) above, likewise form a known class of compounds having many members; any member of which can be suitably used herein. Examples of suitable such imidazoles include imidazole, 2-methyl imidazole, 2-butyl imidazole, 2-decyl imidazole, 4-methyl imidazole, 5-methyl imidazole, 4,5-dimethyl imidazole, benzimidazole, 2-benzyl imidazole, 2-benzyl-4-methyl imidazole, and the like. 2-Methyl imidazole is the most preferred imidazole for use in preparing our new catalysts.
The instant class of catalysts are used in small but catalytic amounts in promoting the reaction between organic isocyanates and organic compounds bearing active hydrogen and reactive with the isocyanates. Normally, amounts of from about 0.1 to about 20 weight percent, based on the weight of isocyanate reactant, is sufficient to yield an acceptable reaction rate at an elevated temperature.
The use of the instant catalyst in the production of polyurethanes is illustrative of their catalytic activity in promoting reaction between isocyanates and organic compounds bearing active hydrogen. The use of the instant catalyst in preparing polyurethanes also represents a preferred use for the instant catalyst. In this utility, any polyol conventionally employed in the preparation of urethanes can be employed in the process of the present invention. Such polyols include polyether polyols, polyester polyols, and the like or mixtures thereof. Such polyols are described in the literature, as illustrated by "Polyurethanes: Chemistry and Technology, parts I and II", by Saunders and Frisch, Interscience, 1964. Particularly suitable polyols include polyether polyols having from 2 to 4 hydroxyl groups per molecule and an average molecular weight of from about 3,000 to about 7,000.
Any organic polyisocyanate conventionally employed in the preparation of urethanes can be employed in the process of the instant invention. This also includes isocyanato-containing prepolymers prepared by reacting various polyols with polyisocyanates and thus producing a product having residual isocyanate groups. Such polyisocyanates are likewise described in the Saunders and Frisch publication mentioned above and also in the patent literature. See, for example, Robins (U.S. Pat. No. 3,583,945), Kamal & Rogier (U.S. Pat. No. 3,455,883), etc. Particularly suitable polyisocyanates include, for example, toluene diisocyanate, methylene diphenyl diisocyanate, and polymethylene polyphenyl isocyanates
In addition to the polyisocyanate and polyol reactants and the instant delayed action catalyst, the thermally curable polyurethane composition may likewise comprise blowing or foaming agents, cell control agents, amine and/or organo-metal catalysts, inert fillers, and the like. Such ingredients are likewise discussed in the Saunders and Frisch publication and the patent literature. Particularly suitable amine catalysts mentioned therein include, for example, triethylenediamine, N-ethylmorpholine, N-(dimethylaminoethyl)piperazine, N-N'-bis(trimethylaminoethyl)piperazine, tetramethylbutanediamine, dimethylethanolamine, bis(2-dimethyl aminoethyl)ether, mixtures thereof and the like. Particularly suitable organo-metal catalysts include stannous octoate, dibutyltin dilaurate, and the like. Other organo-metal catalysts are tin-sulfur catalysts represented by the formula ##STR7## wherein R"1 and R"2 are independently hydrocarbon groups having from 1 to about 8 carbon atoms and R"3 and R"4 are independently hydrocarbon groups having from 1 to about 18 carbon atoms. Such sulfur-containing organo-tin compounds are commercially available from Argus Chemical Corporation as Markure UL-6, Markure UL-29, LRB-1355-331 and LRB-1355-383 and from M and T Chemicals as Thermolite 31.
Methods of formulating the various polyurethanes and the fillers (e.g. silica, aluminum trihydrate, calcium carbonate, barium sulfate, carbon black, mica, titanium dioxide, and the like) are well known to those skilled in the polyurethane art. The following examples, however, will further illustrate the use of the instant catalysts in preparing various polyurethane formulations.
A reaction vessel fitted with a thermometer, water condenser, mechanical stirrer and powder-addition funnel was charged with a solution of 500 g (4.2 mol) of phenyl isocyanate in 1 liter of dry methylene chloride. The methylene chloride was predried with molecular sieves. To this solution was added slowly, and with vigorous stirring, 330 g (4.03 mol) of solid 2-methyl imidazole. The 2-methyl imidazole dissolved instantly in the reaction mixture and reacted readily with the phenyl isocyanate. During the addition, the temperature of the reaction mixture rose from ambient to about 30° C. with a white crystalline product precipitating from solution. The temperature of the reaction mixture was then maintained at about 30° C. by monitoring the rate of addition of 2-methylimidazole to the reaction and by external cooling. Total addition time for the 2-methylimidazole was 1 hour. The reaction mixture thus obtained comprised a white crystalline solid suspended in methylene chloride. This mixture was stirred for an additional 2 hours after all of the 2-methyl imidazole was added. The product was subsequently recovered by filtration, washed twice with 300 ml portions of dry carbon tetrachloride (to remove excess phenyl isocyanate), air dried, and placed in a vacuum oven at room temperature for 12 hours. The product thus obtained was a white crystalline solid weighing 750 g (88.0 percent of theory) and melting at a temperature of from 103°-106° C.
The other catalysts used herein were similarly prepared.
A catalyst corresponding to the structure ##STR8## was prepared by reacting p-chlorophenyl isocyanate with 2-methylimidazole. Two grams of this catalyst was dissolved in 30 ml of tetrahydrofuran (THF). This solution was mixed with 165 g of a urethane prepolymer having an isocyanate equivalent weight of 140. This prepolymer was prepared by reacting an adduct of glycerine and propylene oxide having an average hydroxy equivalent weight of about 86 with toluene diisocyanate in such proportions as to give a product having 30 weight percent reactive isocyanato groups. The THF was subsequently removed from this mixture by vacuum distillation leaving the catalyzed prepolymer as a slightly cloudy liquid.
The above catalyzed prepolymer, 166 g, was blended with (1) 400 g of a polyether polyol mixture containing (a) 90 weight percent of a glycerine-initiated polyoxypropylene glycol capped with ethylene oxide and having an average molecular weight of 4950 and a hydroxy equivalent weight of 1650; and (b) 10 weight percent of diethylene glycol, and (2) 200 g of alumina trihydrate (marketed by the Reynolds Alumina Company under the designation RH31F). These components were mixed in a Kitchen Aid® K45 mixer and frothed at the highest speed of the K45 mixer for 5 minutes. A froth was thus produced having excellent doctorability. A thin layer, 3/16 inch thick, was doctored (i.e. spread) onto a molding board and put into a forced air oven at 120° C. for 5 minutes. When this froth was removed from the oven, it was completely tack-free and cross-linked (i.e. cured). Another sample of the froth was poured into a cup and maintained at room temperature for several minutes. Some temperature rise (up to about 35° C.) was observed but there was no appreciable gelling in the reaction mixture and the froth was still very workable even after 10 minutes
By way of comparison, a conventional catalyst (e.g. triethylene diamine) at a concentration necessary for the final cure in 15 minutes in a 120° C. oven would have gelled in the bowl of the K45 mixer.
The following catalysts were used in place of the p-chlorophenyl isocyanate/2-methyl imidazole reaction product in the above formulation. Each of the following compounds were effective delayed-action, heat-activated catalysts. Compounds 6-10, 12-14 and 16 were particularly effective delayed-action, heat-activated catalysts.
__________________________________________________________________________ Ex. Reactants Catalyst Products __________________________________________________________________________ ##STR9## ##STR10## 4 ##STR11## ##STR12## 5 ##STR13## ##STR14## 6 ##STR15## ##STR16## 7 ##STR17## ##STR18## 8 ##STR19## ##STR20## 9 ##STR21## ##STR22## 10 ##STR23## ##STR24## ##STR25## 11 ##STR26## ##STR27## 2,4 & 2,6-mixture 12 ##STR28## ##STR29## 13 ##STR30## ##STR31## 14 ##STR32## ##STR33## 15 ##STR34## ##STR35## 16 ##STR36## ##STR37## 17 ##STR38## ##STR39## 18 ##STR40## ##STR41## 19 ##STR42## ##STR43## 20 ##STR44## ##STR45## __________________________________________________________________________
other compounds within formula I can be similarly prepared and used.
Claims (9)
1. A composition comprising
a. an organic compound bearing at least one reactive isocyanato group;
b. an organic compound bearing active hydrogen; and
c. a small but sufficient amount of a catalyst to catalyze the reaction between the isocyanato group in (a) and the active hydrogen in (b); said catalyst corresponding to the formula ##STR46## wherein: n is an integer of from 1 to 3; R1 is an n-valent organic radical
R2 is hydrogen, hydrocarbyl or inertly-substituted hydrocarbyl;
R3 and R4 are each independently hydrogen, hydrocarbyl, inertly-substituted hydrocarbyl, or, R3 and R4 are joined to form a 5- or 6-membered carbocylic ring.
2. The composition defined by claim 1 in which (b) is an organic compound bearing alcoholic hydroxyl groups.
3. The composition defined by claim 1 in which (a) is an organic polyisocyanate and (b) is an aliphatic polyol.
4. The composition defined by claim 3 in which (b) is a polyether polyol or a polyester polyol.
5. The composition defined by claim 1 in which R1 is an n-valent carbocyclic aromatic ring or an inertly-substituted n-valent carbocyclic aromatic ring having at least 6 carbon atoms.
6. The composition defined by claim 5 in which R1 is phenyl or an inertly-substituted phenyl and n is 1 or 2.
7. The composition defined by claim 5 in which R1 is phenyl or tolyl.
8. The composition defined by claim 1 in which R3 and R4 are each hydrogen and R2 is methyl.
9. The composition defined by claim 7 in which R1 corresponds to the formula ##STR47## (a) is an organic polyisocyanate having from 2 to 4 isocyanato groups per molecule; and (b) is an aliphatic polyol.
Priority Applications (1)
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US05/624,698 US4041019A (en) | 1975-10-22 | 1975-10-22 | Delayed-action, heat activated-urethane catalyst |
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US05/624,698 US4041019A (en) | 1975-10-22 | 1975-10-22 | Delayed-action, heat activated-urethane catalyst |
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US4041019A true US4041019A (en) | 1977-08-09 |
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US05/624,698 Expired - Lifetime US4041019A (en) | 1975-10-22 | 1975-10-22 | Delayed-action, heat activated-urethane catalyst |
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Cited By (11)
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FR2353579A1 (en) * | 1976-06-01 | 1977-12-30 | Bayer Ag | POLYURETHANES PREPARATION PROCESS |
US4189543A (en) * | 1978-08-21 | 1980-02-19 | The Dow Chemical Company | Catalyst for making polyurethanes |
US4273899A (en) * | 1976-06-11 | 1981-06-16 | Teijin Limited | Fire-retardant thermoplastic polyester composition |
US4452829A (en) * | 1983-06-20 | 1984-06-05 | Thermocell Development, Ltd. | Sprayable, cross-linked trimer polymer and method of use and preparation |
US4469653A (en) * | 1981-07-04 | 1984-09-04 | Basf Aktiengesellschaft | Process for the preparation of molded parts of polyurethane or polyurethane-polyurea employing monocyclic amidines |
US4515846A (en) * | 1984-04-09 | 1985-05-07 | The Dow Chemical Company | Polyurethane backed carpet formed with two catalysts |
EP0193307A2 (en) * | 1985-02-25 | 1986-09-03 | Imperial Chemical Industries Plc | Process for the extraction of metal values and novel metal extractants |
US4797455A (en) * | 1987-08-06 | 1989-01-10 | W. R. Grace & Co.-Conn. | Isocyanates blocked with 1-amino-alkyl imidazoles as epoxy curing agents |
US5159012A (en) * | 1991-11-29 | 1992-10-27 | Textile Rubber & Chemical Co., Inc. | Process for the manufacture of polyurethane elastomers |
US5470986A (en) * | 1994-06-27 | 1995-11-28 | E. I. Du Pont De Nemours And Company | Imidazolium hardeners for hydrophilic colloid |
US20110237742A1 (en) * | 2008-09-29 | 2011-09-29 | E. E. Du Pont De Nemours And Company | Liquid Two-Component Coating Compositions |
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FR2353579A1 (en) * | 1976-06-01 | 1977-12-30 | Bayer Ag | POLYURETHANES PREPARATION PROCESS |
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